The present invention is a process for converting a high-boiling component resulting from the reaction of an organochloride with silicon into commercially more desirable monosilanes. The process comprises contacting the high-boiling component with chlorine at a temperature within a range of about 250.degree. C. to 1000.degree. C. Improved yield of monosilanes can be obtained in the process by the use of a catalyst selected from a group consisting of alumina, silica. activated carbon. AlCl.sub.3, and AlCl.sub.3 supported on a support selected from a group consisting of alumina. silica, and carbon.
The high-boiling component useful in the present process results from a process typically referred to as the "Direct Process,"where an organohalide is reacted with silicon metalloid in the presence of a suitable catalyst to form monosilanes. The Direct Process as described by, for example. Rochow U.S. Pat. No. 2,380,995, issued Aug. 7, 1945 and Barry et al., U.S. Pat. No. 2,488,487, issued Nov. 15, 1949, is the main commercial process by which organohalosilanes (i.e. monosilanes), for example. dimethyldichlorosilane and trimethylchlorosilane are formed. These organohalosilanes are reactive compounds which can undergo numerous reactions to form a variety of useful silicon containing compounds and polymers. A major commercial use of organohalosilanes is in the production of polysiloxane polymers which are useful as heat transfer fluids. lubricants, and the like and which can be further processed, for example, to form silicone elastomers, resins, sealants, and adhesives.
Operation of the Direct Process results not only in the production of the desirable monosilanes, but also in a high boiling component typically considered to be all materials with a boiling point higher than the particular diorganodihalosilane produced in the process. The high-boiling component is a complex mixture that includes compounds containing SiSi, SiOSi. SiCSi, SiCCSi, and SiCCCSi linkages in the molecules. Some typical compounds found in a high-boiling component are described for example, in Mohler et al.. U.S. Pat. No. 2.598,435, issued May 27, 1952, and Barry et al. U.S. Pat. No. 2,681,355. issued Jun. 15, 1954. The high-boiling component may also comprise silicon containing solids and soluble and insoluble compounds of copper, aluminum, and zinc.
In current commercial operations for performing the Direct Process, the high-boiling component can constitute as much as ten percent of the resultant product. Therefore, it is desirable to convert the high-boiling component into commercially desirable products to both reduce low-value byproducts and to improve raw material utilization.
Mohler, U.S. Pate. No. 2,598,435, issued May 27, 1952. describes a process for converting methylpolysilanes present in a Direct Process residue to monosilanes. The process comprises heating the residue at a temperature above 250.degree. C. and below the decomposition point of the formed monosilanes. Of the product recovered approximately 56 weight percent appeared to be monosilanes.
Barry. U.S. Pat. No. 2,681,355, issued Jun. 15, 1954, observed that the process taught in Mohler, U.S. Pat, No. 2,598,435, can result in significant coking of the reactor making the process unsuitable for commercial cracking processes. Barry. supra, teaches that this coking can be reduced if the Direct Process residue is contacted with at least four percent by weight hydrogen chloride at a temperature from 200.degree. C. to 900.degree. C. Barry also suggests that the process can be run in a reactor packed with either an inert material such as quartz or a catalytic material such as activated alumina or silica alumina.
Bluestein, U.S. Pat. No. 2,709,176, issued May 25, 1955, reports a process for converting the polysilanes present in a Direct Process residue into monosilanes by the use of a tertiary organic amine catalyst. Bluestein reports that when the Direct Process residue is contacted with a hydrogen halide and a tertiary organic amine catalyst, the process can be conducted at temperatures of about 75.degree. C. to 150.degree. C. with acceptable yields of monosilanes being obtained.
Gilbert. U.S. Pat. No. 2,842,580, issued Jul. 8, 1958, reports a process for converting the polysilanes present in a Direct Process residue into monosilanes by the use of quaternary ammonium halide and quaternary phosphonium halide compounds as catalysts. The process of Gilbert is run in the absence of hydrogen chloride, as described by Bluestein supra, and is reported to provide monosilanes with reduced levels of hydrogen bonded to the silicon atoms.
The objective of the present process is to provide a process for the conversion of a high-boiling component produced by the Direct Process to monosilanes. To achieve this objective the present process uses chlorine to facilitate conversion of the high-boiling component to monosilanes. Improved yields of monosilanes can be obtained in the process if in addition to the chlorine a catalyst is used selected from a group consisting of alumina, silica. activated carbon, AlCl.sub.3, and AlCl.sub.3 supported on a support selected from a group consisting of alumina. silica, and carbon.